CN110204714B - Magnetic covalent triazine framework material and preparation method and application thereof - Google Patents
Magnetic covalent triazine framework material and preparation method and application thereof Download PDFInfo
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- CN110204714B CN110204714B CN201910540881.9A CN201910540881A CN110204714B CN 110204714 B CN110204714 B CN 110204714B CN 201910540881 A CN201910540881 A CN 201910540881A CN 110204714 B CN110204714 B CN 110204714B
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000013311 covalent triazine framework Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 32
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 6
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 6
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 239000011592 zinc chloride Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000005415 magnetization Effects 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 11
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229960005404 sulfamethoxazole Drugs 0.000 description 7
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013310 covalent-organic framework Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 aromatic nitriles Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract
The invention relates to a magnetic covalent triazine framework material and a preparation method and application thereof, wherein the magnetic covalent triazine framework material comprises a covalent triazine framework and Fe3O4. The magnetic covalent triazine framework material has magnetism, is convenient to recycle, can be used for wastewater treatment, and can be used as a catalyst for degradation of antibiotics. The preparation method of the invention adopts microwave as heat source and Fe3O4As microwave absorbing and transmitting medium, the terephthalonitrile can be rapidly condensed, and simultaneously, Fe3O4The existence of (2) enables the powder to be gathered in the reaction process, and the powder overflow phenomenon is not easy to generate, so that the reaction is more complete.
Description
Technical Field
The invention particularly relates to a magnetic covalent triazine framework material and a preparation method and application thereof.
Background
A Covalent Organic Frameworks (COFs) is a novel high-performance carbonaceous high polymer material which is composed of light elements (H, O, C, N, B) through Covalent bonds with strong bonding force (such as C-C, C-N, C-O and the like), and has high chemical stability in different solvents due to the existence of the Covalent bonds. Covalent triazine-based Frameworks (CTFs) are a class of branches of COFs, and are long-chain polymers having rigid hydrophobic aromatic Frameworks and polar functional groups prepared by using aromatic nitriles as raw materials and ZnCl2The catalyst is prepared by trimerization condensation, and has attracted attention because of no need of organic solvent, low cost, high nitrogen content and the like. The conventional thermal synthesis method requires harsh conditions, requires a long reaction time (20-116h) under the conditions of high temperature and high pressure (400-. The microwave synthesis technology is frequently applied to the field of material preparation due to the advantages of simple operation, short reaction time, high energy utilization rate and the like.
However, the performance of the covalent triazine skeleton material in the prior art still needs to be improved, and in the application process, the problem that the covalent triazine skeleton material is difficult to recover exists.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a magnetic covalent triazine framework material, a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a magnetic covalent triazine framework material which comprises a covalent triazine framework and Fe3O4。
The magnetic covalent triazine framework material is in a regular tetrahedron shape.
The magnetic covalent triazine framework material has superparamagnetism. According to a preferred embodiment, said magnetic covalent triazine backbone material has a saturation magnetization of more than 70emu g-1。
The magnetic covalent triazine framework material of the invention has pores, and further, the magnetic covalent triazine framework material has larger pore diameter and smaller pore volume. According to a preferred embodiment, the pore diameter of the magnetic covalent triazine framework material is 6-8 nm, and the pore volume is 0.02-0.04 cm3·g-1。
According to a preferred embodiment, the surface of the magnetic covalent triazine framework material comprises 46-56% by mass of carbon atoms, 5.5-6.6% by mass of nitrogen atoms, 28-36% by mass of oxygen atoms, 8.9-10.9% by mass of iron atoms and 1.2-1.4% by mass of zinc atoms.
In the invention, the magnetic covalent triazine framework material is powdery.
The invention also provides a preparation method of the magnetic covalent triazine framework material, and the magnetic covalent triazine framework material is prepared from terephthalonitrile and Fe3O4In ZnCl2Under the action of microwave, the product is obtained.
In the invention, Fe is adopted3O4The microwave absorbing and transmitting medium is used together with microwaves, so that the reaction temperature can be ensured to carry out the reaction; in addition, by adjusting different microwave output powers, the microwave power is adjustedThe properties of the generated magnetic covalent triazine framework material are different, so that the magnetic covalent triazine framework material can be applied to different fields.
Preferably, the output power of the microwave is 300-600W, so that the reaction can be fully performed, and the utilization rate of raw materials is improved.
Preferably, said terephthalonitrile and Fe3O4The charging molar ratio of (a) to (b) is 1:0.5 to 1.2, and more preferably 1:1 to 1.2. The product performance can be better by adopting the feeding molar ratio while taking the yield into consideration.
Preferably, said terephthalonitrile and said ZnCl2The feeding mass ratio of (A) to (B) is 1: 5-10. The residual quantity of the zinc salt in the product can be reduced by adopting the mass ratio while taking the yield into consideration.
According to a preferred and specific embodiment, the preparation method is as follows: reacting said terephthalonitrile, said Fe3O4And said ZnCl2And after mixing, reacting for 30-90 min under the microwave power of 300-600W, soaking with hydrochloric acid, separating precipitates under the condition of an external magnetic field, and washing and drying the precipitates to obtain the magnetic covalent triazine framework material.
The third aspect of the invention provides the application of the magnetic covalent triazine framework material in wastewater treatment.
In particular, the magnetic covalent triazine framework material adsorbs harmful substances such as methylene blue, dye and the like in wastewater.
The third aspect of the invention provides the application of the magnetic covalent triazine skeleton material in the degradation of antibiotics, wherein the magnetic covalent triazine skeleton material and an oxidant are added when the degradation of the antibiotics is carried out.
Wherein, the magnetic covalent triazine framework material is used as a catalyst.
The raw materials in the present invention may be commercially available, or Fe in the present invention3O4Prepared by a hydrothermal method.
Hydrothermal method for preparing Fe3O4Specific method of (1)Comprises the following steps: 6.74g FeCl was weighed3·6H2And placing the O into 125mL of ethylene glycol, stirring for 30min to obtain a homogeneous solution, adding 14.37g of sodium acetate, continuously stirring for 30min, uniformly mixing, transferring the mixed solution into a 200mL high-pressure reaction kettle, and reacting for 8h at 200 ℃. After cooling to room temperature, the black magnetic microspheres were collected with a magnet, washed three times with water and ethanol alternately, vacuum dried at 60 ℃ for 6h, and ground for future use.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the magnetic covalent triazine framework material has magnetism, is convenient to recycle, can be used for wastewater treatment, and can be used as a catalyst for degradation of antibiotics.
The preparation method of the invention adopts microwave as heat source and Fe3O4As microwave absorbing and transmitting medium, the terephthalonitrile can be rapidly condensed, and simultaneously, Fe3O4The existence of (2) enables the powder to be gathered in the reaction process, and the powder overflow phenomenon is not easy to generate, so that the reaction is more complete.
Drawings
FIG. 1 is an SEM (left) and TEM (right) image of MCTF obtained in example 5;
FIG. 2 is an FTIR spectrum of MCTF and terephthalonitrile (DCB) obtained in example 5;
FIG. 3 is an XRD pattern of MCTF obtained from example 5;
FIG. 4 is a magnetization curve of MCTF obtained in example 5;
FIG. 5 is an XPS plot of MCTF obtained in example 5;
FIG. 6 is a graph showing N in MCTF obtained in example 52Adsorption-desorption isotherms;
FIG. 7 shows MCTF, DCB and Fe3O4Adsorption rate curve to AO 7;
FIG. 8 shows the degradation trend of SMX in different systems;
figure 9 is a graph of the tendency of MCTF prepared in various examples to catalyze PMS to degrade SMX.
Detailed Description
The technical solution of the present invention will be described in further detail below with reference to specific embodiments.
Fe described below3O4From Mecline I811693-500 g; terephthalonitrile was purchased from alatin D111053; zinc chloride was purchased from Meclin Z820755. The following examples employ microwave equipment from Shanghai New Instrument microwave chemistry, Inc. (Uwave-2000).
Example 1
Weighing 2g of terephthalonitrile and 2g of Fe3O4Mixing uniformly, and quickly adding 16g ZnCl2Uniformly mixing, transferring the powder into a quartz crucible, reacting for 60min under the power of 500W to obtain a black product, and reacting with the black product at the power of 0.1 mol.L-1HCl soak to remove residue while preventing ZnCl2Hydrolyzing, separating precipitate under the condition of external magnetic field after soaking, washing with water and anhydrous ethanol alternately for three times, vacuum drying at 60 deg.C for 6 hr, taking out, and grinding to obtain 0.85g MCTF powder.
Example 2
Weighing 2g of terephthalonitrile and 4g of Fe3O4Mixing uniformly, and quickly adding 16g ZnCl2Uniformly mixing, transferring the powder into a quartz crucible, reacting for 60min under the power of 300W to obtain a black product, and reacting with the black product at the power of 0.1 mol.L-1HCl soak to remove residue while preventing ZnCl2Hydrolyzing, separating precipitate under the condition of external magnetic field after soaking, washing with water and anhydrous ethanol alternately for three times, vacuum drying at 60 deg.C for 6h, taking out, and grinding to obtain 2.93g MCTF powder.
Example 3
Weighing 2g of terephthalonitrile and 4g of Fe3O4Mixing uniformly, and quickly adding 16g ZnCl2Uniformly mixing, transferring the powder into a quartz crucible, reacting for 60min under 400W power to obtain a black product, and reacting with the black product at 0.1 mol.L-1HCl soak to remove residue while preventing ZnCl2Hydrolyzing, separating precipitate under the condition of external magnetic field after soaking, washing with water and anhydrous ethanol alternately for three times, vacuum drying at 60 deg.C for 6 hr, taking out, and grinding to obtain 2.68g MCTF powder.
Example 4
Weighing 2g of terephthalonitrile and 4g of Fe3O4Mixing uniformly, and quickly adding 16g ZnCl2Uniformly mixing, transferring the powder into a quartz crucible, reacting for 60min under the power of 500W to obtain a black product, and reacting with the black product at the power of 0.1 mol.L-1HCl soak to remove residue while preventing ZnCl2Hydrolyzing, separating precipitate under the condition of external magnetic field after soaking, washing with water and anhydrous ethanol alternately for three times, vacuum drying at 60 deg.C for 6h, taking out, and grinding to obtain 1.54g MCTF powder.
Example 5
Weighing 2g of terephthalonitrile and 4g of Fe3O4Mixing uniformly, and quickly adding 16g ZnCl2Uniformly mixing, transferring the powder into a quartz crucible, reacting for 60min under 600W power to obtain a black product, and reacting with the black product at the power of 0.1 mol.L-1HCl soak to remove residue while preventing ZnCl2Hydrolyzing, separating precipitate under the condition of external magnetic field after soaking, washing with water and anhydrous ethanol alternately for three times, vacuum drying at 60 deg.C for 6h, taking out, and grinding to obtain 1.24g MCTF powder.
The SEM and TEM of the MCTF powder are shown in FIG. 1, and it can be seen that the powder is in the form of regular tetrahedrons with well-defined corners and clearly visible boundary marks.
Analysis of functional groups of MCTF and the starting material DCB by FTIR, as shown in FIG. 2, the DCB starting material for the synthesis of MCTF contained a-C.ident.N bond, and therefore had a spectrum of 2232cm in DCB-1Has obvious vibration peak, compared with MCTF which has no vibration peak at 1613cm-1And 1411cm-1The peak appears when the C-N bond and the C-C bond vibrate, which proves that the triazine ring exists and the trimerization reaction is completed, 588cm-1The peak is Fe-O vibration peak.
In order to investigate the composition of the ferrite compounds, XRD of MCTF was analyzed as shown in FIG. 3, showing strong diffraction peaks at diffraction angles of 18.3 °, 30.4 °, 35.4 °, 37 °, 43 °, 53.3 °, 56.8 °, 62.4 °, peak positions corresponding to Fe3O4Standard cards (JCPDS75-1609) conform to, which correspond to Fe respectively3 O 4111, 220, 311, 222, 400, 422, 511, and 440 of MCTF, it was confirmed that the magnetic iron oxide contained in MCTF was Fe3O4。
By measuring the saturation magnetization of MCTF at room temperature, as shown in FIG. 4, it can be seen that there is no obvious hysteresis loop, the magnetization curve is S-shaped, no hysteresis phenomenon occurs, and the material shows good superparamagnetism. The saturation magnetization of MCTF was 75.14emu g-1And has good magnetic performance.
FIG. 5 is an XPS diagram of MCTF, in which 284.1eV, 398.1eV and 530.1eV, three peaks with stronger signals appear, which correspond to the bonding energies of C1s, N1s and O1s in MCTF, and show that the main elements of the surface of the material are carbon, nitrogen and oxygen. Meanwhile, a weaker Zn2p peak appears at 1021.1, which indicates that excessive ZnCl exists in the material synthesis process2So that a certain amount of ZnCl remains even by washing with hydrochloric acid for a long time2. The atomic mass percentages of the MCTF are shown in Table 1, and it can be seen from Table 1 that the material contains ZnCl2 residue, but the atomic mass of Zn is only 1.31%.
TABLE 1
| Name (R) | C | N | O | Fe | Zn |
| Atomic mass% | 50.63 | 6.05 | 32.15 | 9.85 | 1.31 |
The porosity of MCTF was evaluated by nitrogen uptake experiments at 77K, and FIG. 6 shows the N of MCTF2Adsorption-desorption isotherms, which showed the isotherm of type IV, were observed, and the presence of a hysteresis loop was confirmed, demonstrating that the material has a large number of micropores and a BET specific surface area of 93.6131m2·g-1But has a pore diameter of 6.93nm and a pore volume of 0.03cm3·g-1The larger pore size and smaller pore volume of the material enable the material to have the potential of storing substances and maintaining the activity of the substances.
Application example 1 methylene blue adsorption experiment
5mL of methylene blue (10 mg. L) was taken-1) 10mg of the MCTF materials prepared in examples 2 to 5 were added into a centrifuge tube, and after vortexing for 30 seconds, the absorbance of the raffinate was measured by an ultraviolet-visible spectrophotometer, and the absorbance was substituted into a standard curve to calculate the methylene blue concentration of the raffinate, and the adsorption rate was calculated by the following formula, and the results of the adsorption rate of the MCTF materials prepared in each example are shown in Table 2.
Adsorption rate (%) - (c)0-ct)×100/c0
TABLE 2
| Example 2 | Example 3 | Example 4 | Example 5 | |
| Adsorption rate | 57.4％ | 63.3％ | 96.9％ | 93.1％ |
Application examples 2, AO7 adsorption experiment
100mL of AO7 working solution (10 mg. L) was taken-1) In a conical flask, 0.1 mol.L is used-1HCl and NaOH to adjust the initial pH of the solution. Prepared MCTF (obtained in example 3), DCB and Fe were separately mixed3O4The timing is started when the solution is put into the prepared solution, and the magnetic stirring speed is adjusted to be about 1000 r.min-1The MCTF is thrown out at high speed without being attached to the surface of the rotor and is uniformly distributed in the solution, and 5mL of the solution is taken at different time points and is filtered by a 0.45-micron water system filter film to be measured.
MCTF, DCB and Fe3O4The adsorption rate of AO7 is shown in FIG. 7, wherein T298K and C (AO7) 10 mg.L are measured-1,pH≈7，C(MCTF、DCB、Fe3O4)＝0.4g·L-1。
Within 20min, terephthalonitrile and Fe3O4The adsorption rates of AO7 were 3.0% and 3.4%, respectively, under the system. From this, it can be seen that the raw materials terephthalonitrile and Fe3O4No significant adsorption on AO 7; compared with the prior art, the MCTF has the adsorption rate of 98.8 percent on AO7 within 20 min.
Application example 3 SMX degradation experiment
At room temperature, a predetermined amount of pure water was poured into a 100mL volumetric flask, and a predetermined amount of Peroxymonosulfate (PMS) and MCTF (obtained in example 4) were added to bring the reaction concentrations to 0.15 mmol.L, respectively-1、0.3g·L-1Subsequently, a certain amount of Sulfamethoxazole (SMX) was added to bring the reaction concentration to 0.5 mmol. multidot.L-1The reaction starts. Samples were taken at different time points, followed by rapid addition of excess quencher Na2S2O3The reaction was stopped and the quenched sample was filtered through a 0.22 μm filter and the filtrate was collected and analyzed by HPLC-MS/MS. For comparative analysis, blanks were PMS alone and MCTF alone. The results are shown in fig. 8, where T298K and c (smx) 0.5mmol · L were measured-1,pH≈7，C(MCTF)＝0.3g·L-1，C(PMS)＝0.15mmol·L-1。
As can be seen from FIG. 8, PMS and MCTF alone have no obvious effect, and PMS added as oxidant and MCTF added as catalyst SMX can be completely degraded within 30 min.
Meanwhile, the MCTF materials prepared in different examples are examined for the effect of catalyzing the PMS to degrade SMX, as shown in FIG. 9, wherein 300W is example 2, 400W is example 3, 500W is example 4, and 600W is example 5, as can be seen from FIG. 9, example 5(600W) has the best effect, and can be completely degraded within 30 min.
The present invention is described in detail in order to make those skilled in the art understand the content and practice the invention, and the invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the invention should be covered by the scope of the invention.
Claims (8)
1. A magnetic covalent triazine scaffold material, characterized by: comprising a covalent triazine skeleton and Fe3O4(ii) a The magnetic covalent triazine framework material is prepared from terephthalonitrile and Fe3O4In ZnCl2Under the action of microwave, the magnetic covalent triazine skeleton material is in a regular tetrahedron shape; the magnetic covalent triazine framework material has superparamagnetism, and the saturation magnetization intensity of the material is more than 70emu-1(ii) a The magnetic covalent triazine framework material has pores, the pore diameter of the pore is 6-8 nm, and the pore volume is 0.02-0.04 cm3•g-1。
2. A process for the preparation of a magnetic covalent triazine framework material as claimed in claim 1, characterized in thatCharacterized in that: the magnetic covalent triazine framework material is prepared from terephthalonitrile and Fe3O4In ZnCl2Under the action of microwave, the product is obtained.
3. The method of claim 2, wherein: the output power of the microwave is 300-600W.
4. The method of claim 2, wherein: the terephthalonitrile and Fe3O4The feeding molar ratio of (A) to (B) is 1: 0.5-1.2.
5. The method of claim 2, wherein: said terephthalonitrile and said ZnCl2The feeding mass ratio of (A) to (B) is 1: 5-10.
6. The method of claim 2, wherein: the preparation method comprises the following specific implementation modes: reacting said terephthalonitrile, said Fe3O4And said ZnCl2And after mixing, reacting for 30-90 min under the microwave power of 300-600W, soaking with hydrochloric acid, separating precipitates under the condition of an external magnetic field, and washing and drying the precipitates to obtain the magnetic covalent triazine framework material.
7. Use of a magnetic covalent triazine framework material of claim 1 in wastewater treatment.
8. Use of a magnetic covalent triazine scaffold material according to claim 1 for the degradation of antibiotics, wherein said magnetic covalent triazine scaffold material and an oxidizing agent are added during the degradation of antibiotics.
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